Epoxy esters of 3, 4-epoxy-cyclohexane-1-carboxaldehyde acetals



Patented Oct. 19, 1965 3,213,111 compounds of the formula EPOXY ESTERS F3,4-EPOXY-CYCLOHEXANE-1- CARBOXALDEHYDE ACETALS Hans Batzer, Rainweg 7,Arlesheim, Switzerland; Willy C 0 0 C Flsch, Stelzenackerstrasse 11,Binningen, Switzerland; 5 and Erwin Nikles, Untere Rebgasse 16, Basel, 5fi /CH C Switzerland 0 l 8 0 O 0 bio Drawing. Filed Sept. 3, 1963, Ser.No. 306,281 Claims priority, application Switzerland Sept. 17, 1959,

78,334/59; Mar. 25, 1960, 3,374/60 B4 0 R1 R1 G R4 4 Claims. (Cl.260-3403) 10 R5 Ra Ra Ra This application is a continuation-in-part ofapplica- (11) tion Serial No. 54,582, filed September 8, 1960 and nowabandoned. compounds of the formula R2 l R1\ /R1 R3 \C /Ra/O\ /O\ Rn\/C\ /R3 o \CCH ZO-C Y o-o-z 011-0 0 u L Jrl n 0 R3 0 O O 0 R3\ /0 \C R5Ra Ra Ra The present invention provides new acetals that containcompounds of the formula at least two epoxide groups and correspond tothe formula R2 R1 (1) Ra\ /C\ /Rg/O\ R /0 0-05 /Z-O("3A1 o o o z-o- 0 l1 R8 0 O 0 R\O/ Y \C a C 4 /C\ R7 R5 at (W) n and compounds of theformula 0 in which R to R each represents a hydrogen atom or amonovalent snbstituent such as a holagen atom, an alkoxy group or analiphatic, cycloaliphatic, araliphatic or aro- 0 0-03 z 0- rnatichydrocarbon radical, and R and R together may also represent an alkyleneradical such as a methylene a group; Z represents a trivalent aliphatic,cycloaliphatic or araliphatic hydrocarbon radical with at least 3 carbonc 31 atoms, none of which has more than a single free valence, R6 (V)and no carbon atom having such a free valence carries a in which R andtaken together form a member h d l ;G r ent r0 1 5 y foxy group rep 65 Sa g up selected from the class consisting of two hydrogen atoms, twolower alkyl radicals having 1 to 4 carbon atoms, and one methyleneradical, R R R R R7, R and R each 0, 0:0 or 0:0 represents a memberselected from the class consisting of hydrogen atom and lower alkylgroup having 1 to 4 car- 0 hon atoms, Z represents thehydrocarbonradical of a trin is a small whole number and Y represents analiphatic, hydfic aliphatip i Y .represeints the hydrocarboncycloaliphatic, araliphatic or aromatic radical with n free radical of adlcarbQXYhc acid A1 a menber Select/ed valences and when N21 the radicalY must contain at from 9135s conslstmg of epoxya kyl an d alkyl, A 1s amember selected from the class consisting least one e oxide rou More particular ly, the present invention provides new of epoxyalkylepoxycycloalkyl and the radlcal of the diepoxide compounds of theformulae formula /OCH2 /CE2 S --CHGHz-OH o 011 it ow o 0 0-05 zoz /CHC oRfloH CE 0/ Rs 0 0 Rs l 1 O g C 2 (v1 where R is selected from the classconsistlng of hydrogen atom and the methyl group, and n represents aninteger R5 R5 R6 R5 (1) of at least 1 and at the most 2.

The acetals containing epoxide groups of the present process areobtained by treating an unsaturated acetal of R5 Rs 11 in which R to RZ, G and n have the same meanings as in the formula (I) and Y representsan aliphatic, cycloaliphatic, araliphatic, or aromatic radical and, whenn=1, the radical Y contains at least one epoxidizable group or anepoxide group-with an epoxidizing agent.

The term epoxidizable group refers above all to residues containingepoxidizable carbon-to-carbon double bonds, such as an allyl, butenyl ortetrahydrobenzyl radical; by treating such carbon-to-carbon doublebonds, for example with organic per-acids, they can be epoxidized toform the 1:2-epoxide group.

The term epoxidizable group further designates radicals containing ahalohydrin grouping in which Hal represents a halogen atom, such as a,6- methylglycerol-a-monochlorohydrin radical or aglycerola-mono-chlorohydrin radical. It is known that such a halohydringroup can likewise be converted into a 1:2- epoxide group by treatmentwith a dehydrohalogenating agent.

The starting materials of the Formula (II) are obtained, for example,when in a first stage an aldehyde of the formula 2 B3 \c/ R9 H L l Rs 0o 0 Ri o R7 115 \R6 (III) is acetalized with a polyalcohol of theformula z o' 110 (IV) The third functional group G in the polyalcohol(IV) is preferably likewise a hydroxyl group, but it may also representa halogen atom, such as chlorine or bromine, or 1 group in the presenceof an acid catalyst such, for example, as hydrochloric acid orpara-toluenesulfonic acid.

Furthermore 1 mole of an aldehyde of the Formula (III) may be added onto 1 mole of an epoxide of the formula (V) In either case the reactionproduct is an acetal of the formula The conversion of the compound (VI)into the unsaturated acetal of the Formula (II) depends on the nature ofthe functional group G. A suitable method is condensation, such asetherification, esterification or reesterification with a reactivecompound containing, for example, one or more mobile halogen atoms, orgroups containing active hydrogen atoms. Likewise suitable is anadditive combination of an anti-unsaturated compound with one or severalcarbon-to-carbon double bonds.

In this connection two basically different cases must be distinguished:

(l) The reactive compound used for the reaction with the acetal (VI)contains an epoxide group or an epoxidizable group, for example anepoxidizable carbon-to-carbon double bond which does not participate inthe reaction with the acetal (VI). In this case it is possible to usereactive compounds containing only one reactive group such, forexam-pie, as a mobile halogen atom, a hydroxyl or carboxyl group.

(2) The reactive compound used is free from epoXide groups orepoxidizable groups that do not undergo reaction already with the acetal(VI). In this case the reactive compounds must contain at least tworeactive groups, such for example, as mobile halogen atoms, hydroxyl orcarboxyl groups or olefinic carbon-to-carbon double bonds capable ofaddition on to hydroxyl groups or the like.

In case (1) there may be mentioned as compounds that contain epoxidegroups or are epoxidizable and contain a reactive group as definedabove: e-pihalohydrins such as epichlorohydrin; dihalohydrins such asglycerol dichlorohydrins; unsaturated alcohols such as allyl alcohol, A-tetrahydrobenzy1 alcohol and 6-methyl-A -tetrahydrobenzyl alcohol;glycerol diesters of unsaturated fatty acids such as glycerol dioleateor glycerol dilinoleate; unsaturated carboXylic acids and functionalderivatives thereof such as A -tetrahydrobenzoic acid, 6-methyl-A-tetrahydrobenzoic acid, oleic acid, elaidic acid, ricinoleic acid,linoleic acid, ricinenic acid, tall oil acids, soybean fatty acids,linseed oil acids, tung oil acids, crotonic acid, acrylic acid,methacrylic acid, acrylic acid methyl ester, acrylyl chloride and thelike; unsaturated halides, such as allyl bromide and allyl chloride;unsaturated acetals, such as 3-vinyl-2:4-dioxospiro(5:5)undecene-8 and3- propenyl-7-methyl-2 4-dioxospiro (5 5 undecene-S.

In case (2) there may be mentioned as saturated or unsaturated compoundscontaining at least two reactive groups as defined above: Saturatedpolyalcohols such as ethylene glycol, diethylene glycol, triethyleneglycol, butanediol-l:4, glycerol, sorbitol, penta-erythritol;unsaturated poly-alcohols such as butene-(2)-diol-1:4, 1:1-bis-[hydroxyethyl]-cyclo-hexene-3 and lzl-bis-[hydroxymethyl] 6methylcyclohexene 3; glycerol monoesters of unsaturated fatty acids suchas glycerol monooleate or glycerol monolinoleate; diphenols andpolyphenols such as fesorcinol, hydroquinone, 'bis-[para-hydroxyphenyl]-hydrolyzed, that is to say compounds in which the epoxide methane and2:2-bis-[para-hydroxyphenyl]-propane; cargroup of the poly-epoxide ofthe Formula (I) has been bonic acid, phosgene and polycarboxylic acids,such as Wholly or partially hydrolyzed to hydroxyl groups. oxalic,succinic, adipic, sebacic, hexahydrophthalic, It has been observed thatthe presence of such byphthalic, terephthalic, maleic, fumaric,tetrahydro- 5 products generally has a favorable influence on thetechniphthalic, pyromellitic acid and functional derivatives calproperties of the cured polyepoxides. It is therefore, thereof such astheir acid halides and acid anhydrides; in general, advantageous not toisolate the pure polyfurthermore polyhalogen compounds such asdichloroepoxides from the reaction mixture.

methane, dichloroethane, dibromoethane, dichlorobutene Particularlyadvantageous technical properties are and the like; also compoundscontaining two or more found, for example, in the diepoxides of theformula /Cga /O -CH2 CH CHE-CE [-CH :lO[[-("1-Y1] CE 0/ 0 2 0 mit CH; O[/0 on /CHR RC\H /CH CH1 CH2 carbon-to-carbon double bonds capable ofadding on to in which R and R each represents a hydrogen atom or ahydroxyl groups with formation of an ether bridge, such lower alkylradical with 1 to 4 carbon atoms, Y an alias ethylene glycol-bis-acrylicacid esters, N:N-bis-[acrylphatic, cycloaliphatic, araliphatic oraromatic hydrocarbon amido1-methane andNzN:N-triacrylyl-hexahydroradical, and m and n eachzl or 2; also in thediepoxides triazine-1z3z5; and bisacetals of acrolein, such as 3:9- ofthe formula divinyl-spiro-bi-(meta-dioxane). CH2 0 CH2 Furthermore,unsaturated acetals of the Formula (II) II can be prepared directly byacetalizing 2 moles of an CH CH GH O C CH g aldehyde of the Formula(III) with 1 mole of a poly- I I 0- CH2 I /0 alcohol of the formula CHCH-R R'CH CH ohz 0111 (X) ZG-Z\ in which R and R each represents ahydrogen atom or a OH (v11) lower alkyl radical with 1 to 4 carbonatoms.

Such epoxides are bright resins which are at room temperature liquid orfusible and can be converted with suitable curing agents such, forexample as dicarboxylic acid anhydrides, into clear and bright, curedproducts having excellent technical properties.

The epoxidized acetals of the invention react with the conventionalcurers for epoxides compounds; they can As examples of poly alcohols(VII) there may be mentioned diglycerol and ethylene glycol-diglycericether.

Finally, unsaturated acetals of the Formula (II) may also be prepareddirectly by acetalizing 1 mole of an aldehyde of the Formula (III) with1 mole of a dialcohol of the formula HO 4 therefore be cross-linked orrespectively cured in the presence of such curing agents in the samemanner as other (VIII) polyfunctional epoxide compounds or epoxy resinsrespectively. As such curing agents there may be mentioned in which theradical Y contains an epoxidizable group. basic or more espaciamy acidiccompounds Examples of dialcohols (VIII) are: Adducts of triols, Thefollowing have proved Suitable; Amines d Such as glycerol withdtcyclopehtedlehe Dlels'Alder amides, such as aliphatic and aromaticprimary, secondary ducts of monoallyl ethers of triols, such asglyceroland tertiary amines, f example mom), and tributyp mohahyl ether,wlth cyetopehtadleheamines, para-phenylenediamine,bis-[para-aminophenyl]- 111 the Process of the Present h he acetals ofmethane, ethylenediamine, N:N-diethylethylenediamine, the are treatedwlth epOXldlZlhg hgehts- 5O diethylenetria mine, tetra [hydroxyethyl]diethylenetri- Theepoxldatlon f e carbOn-to-carbon double b d amine,triethylenetetramine, tetraethylenepentamine, leadmg t0 the eompohhds otthe Present lhvehttoh 1S N:N-dimethylpropylenediamine, trimethylamine,diethyl- Performed y a fiehvehtlfmal method, P e y with h amine,triethanolamine, Mannichs bases, piperidine, piald Of all ol'gahle P has p PeIhehZOlC, perazine, guanidine and guanidine derivatives such asPeradipie, moho-perphthahe held the further phenyl diguanidine,diphenylguanidine, dicyandiamide, Suitable epoxtthling agent ishypoehtorohs held, h a first formaldehyde resins with aniline, urea andmelamine; Stage H001 helhg fldded t0 e double bond and 111 a e polymersof aminostyrenes, polyamides, for example those 011d Stage the ePOXIdegroup h h formed under the acttoh prepared from aliphatic polyamines anddimerized or of an agent Capable of sphttlhg Ott hydrogen ehtonde,trimerized unsaturated fatty acids, isocyanates, isoth-iofor example aStrong alkah cyanates; polyhydric phenols, for example resorcinol, Incorrespondence with what has been said above conhydroquinone, bi 4 h d-h 1 -di h l h g the Significance 0f the term iepoxidllahte group"quinone, phenol-aldehyde resins, oil-modified phenol-aldethe treatmentaccording to the invention with ePOXidiZh'Ig hyde resins; reactionproducts of aluminum alcoholates agents includes also reaction withagent Capable of and phenolates with compounds of tautomeric reactionSplitting 0ft y e halide, Such as Potassium hydroxide of the type of theacetoacetic esters, Friedel-Crafts cataor sodium hydroxide, uponhalohydrin groups, for e lysts such as aluminum chloride, antimonychloride, tin ample the g y moheehlofohydfih P, to form thetetrachloride, zinc chloride, boron trifiuor'ide and comcorrespondlng1:2-ep0xide group or a glycidyl group. plexes thereof with organiccompounds; metal fluoborates Wh the aeetal 0f the Formula contains inand phosphoric acid. Preferred curing agents are polydition toepoxidizable carbon-to-carbon double bond basic carboxylic acids andanhydrides thereof, for examhalohydrln groups, the epoxidation takesplace in two ple phthalic anhydride, methylendomethylene-tetrahystages.drophthalic anhydride, dodecenyl succinic anhydride,

The epoxidation may yield, in addition to the diepoxhexahydrophthalicanhydride, hexachloro-endomethyleneides or polyepoxides respectively, byway of side reactetra-hydrophthalic anhydride orendomethylene-tetrahytions also epoxides that are wholly or onlypartially drophthalic anhydride, or mixtures thereof; maleic or succinicanhydr-ide. If desired, an accelerator, such as a tertiary amine or astrong Lewis base, for example an alkali metal alcoholate, andadvantageously also a polyhydroxy compound, such as hexanetriol orglycerol, may be further added.

It has been observed that when an epoxy resin of the invention is curedwith a carboxylic anhydride it is of advantage to use for every gramequivalent of epoxide groups only about 0.3 to 0.9 gram equivalent ofanyhydride groups. When a basic accelerator is used, such as an alkalimetal alcoholate or an alkali metal salt of a carboxylic acid, up to 1.0gram equivalent of anyhydride groups may be used.

The term curing as used in this context signifies the conversion of theaforementioned epoxide compounds into insoluble and inf-usible resins.

Accordingly, the present invention also includes curable mixturescontaining an epoxidized acetal of the invention as well as a curingagent for epoxy resins, preferably a dior polycarboxylic acid anhydride.

Advantageously, the curable mixtures of the invention further contain ashare of otherwise suitable acetals Whose expoxide groups however havebeen wholly or partially hydrolyzed to hydroxyl groups, and/ or alsoother crosslinking poly-hydroxy compounds, such as hexanetriol. It is,of course, possible to add to the curable epoxide compounds also otherepoxides such, for example, as monoglycidyl or polyglycidyl ethers ofmonoalcohols or polyalcohols such as butanol, 1:4-butanediol orglycerol, or of monophenols or polyphenols such as resorcinol, bis- [4hydroxyphenyl] dimethylmethane or condensation products of aldehydeswith phenols (novolaks); also polyglycidyl esters of polycarboxylicacids such as phthalic acid; also aminopolyepoxides such as are obtainedfor example by dehydrohalogenating a reaction product of anepihalohydrin with a primary or secondary amine, such as n-butylamine,aniline or 4:4'-di-(monomethylamino) -diphenyl-methane.

Furthermore, the curable epoxide compounds or mixtures thereof withcuring agents can be admixed at any stage prior to the curing withfillers, plasticisers, coloring matters and the like. Suitable extendersand fillers are, for example, asphalt, bitumen, glass fibers, mica,quartz meal, cellulose, kaolin, finely dispersed silicic acid (Aerosil)or metal powders.

The mixtures of the epoxide compounds of the invention with the curingagent can be used without or with fillers, if desired in the form ofsolutions or emulsions, as textile, assistants, laminating resins,paints, lacquers, dipping resins, casting resins, coating compositions,pore fillers and putties, adhesives, moulding compositions or the like,as well as for the manufacture of such products. The new resins areespecially valuable for use as insulating compounds for the electricalindustry.

In the following, parts and percentages are by weight, the relationshipbetween part by Weight and part by volume being the same as that betweenthe kilogram and the liter.

PREPARATION OF THE INTERMEDIATES M-tefiahydrobenzal glycerol A solutionof 184 parts of glycerol, 220 parts of A tetrahydrobenzaldehyde and 4parts of para-toluenesulfonic acid in 500 parts by volume of benzene isheated in a cyclic distillation apparatus (described by Batzer andco-workers in Makromolekulare Chemie 7, (1951) page 82) until (afterabout 20 hours) 25 parts by volume of Water have separated; theremainder of the water of reaction is absorbed by the drying agent. Thecooled solution is agitated with 100 parts by volume of water and thenwith 50 parts by volume of sodium carbonate solution, dried over sodiumsulfate and the benzene is evaporated. The residue is subjected tofractional distillation, to yield 290 parts of a main fraction (=75% of6-me'fhyl-A -tetrahydrobenzal glycerol Acetal: B.P. about C. under 0.4mm. Hg pressure.

C H O Calculated: C, H, 9.15%- C, 66.46; H, 9.14%.

Acetal from A -tetrahydrobenzaldehyde and 1:2 :6- hexanetriol Acetal:B.P. 126128 C. under 0.08 mm. Hg pressure.

C H O Calculated: C, 68.99; H, 9.80%. Found: C, 69.15; H, 10.03%.

2:S-endomethylene-A -tetrahydrobenzal glycerol Found:

244 parts of 2:S-endomethylene-A -tetrahydrobenzaldehyde and 184 partsof glycerol are condensed in a cyclic distillation apparatus in thepresence of 500 parts by volume of benzene, 1 part of anhydrous zincchloride and 1 part by volume of concentrated phosphoric acid, with 33parts of water separating out. The solution is filtered and evaporatedand the residue is distilled in a high vacuum, to yield 310 parts of thecyclic acetal boiling at 97-100 C. under 0.04 mm. Hg pressure.

C H O Calculated: C, 67.32; H, 8.22%. Found: C, 67.18; H, 8.26%.

When equivalent amounts of aldehyde and triol are condensed as describedabove, the following products are obtained:

Acetal from 6-methyl-A -tetrahydrobenzaldehyde and 1 :2 :4-butanetri0lB.P. 103-105 C. under 0.2 mm. Hg pressure.

Acetal from 6-methyl-A -tetrahydrobenzaldehyde and 1 :1 :1-trimethyl0lpr0pane B.P. 119-120" C. under 0.2 mm. Hg pressure.

In the following examples of the performance of the present processcommercial peracetic acid of about 42% strength has been used; itcontains in addition to acetic acid about 3% of hydrogen peroxide, 10%of water and 1% of concentrated sulfuric acid. Unless otherwiseindicated, the sulfuric acid is neutralized prior to use with about 2%of anhydrous sodium acetate.

EXAMPLE 1 198 parts of 6-methyl-A -tetrahydrobenzal glycerol are addeddropwise at 2-10 C. to a solution of 49.5 parts of phosgene in 800 partsby volume of anhydrous benzene. The mixture is allowed to heat up toroom temperature, the pyridine hydrochloride is filtered off and thefiltrate is washed in the cold with 2 N-hydrochloric acid, 2 N-sodiumhydroxide solution and a molar monosodium phosphate solution. Thesolution is dried over anhydrous sodium sulfate, filtered andevaporated, Whereby the carbonate is obtained as a highly viscousliquid.

For analytical purposes a specimen of the product is distilled.

158 parts of the unsaturated carbonate are dissolved in 675 parts ofethyl acetate and the solution is treated with 163 parts of peraceticacid. The mixture is first C. under 0.02 mm. Hg pressure,

Found:

9 cooled and then heated to and maintained at 40 C. After /2 hours thetheoretical amount of peracetic acid has been consumed. The whole isdiluted with 500 parts by volume of ethyl benzene, washed twice with 100parts of water on each occasion and evaporated in a water-jet vacuumafter having been diluted with 2000 parts by volume of ethyl benzene.The residue is an amorphous resin containing 3.60 epoxide equivalentsper kg.

The epoxide compound obtained by the procedure of this example has theformula 0 CH O-CH o o11o 3 t'nm-o-iLo-dm EXAMPLE 2 A mixture of 396parts of 6-methyl-A -tetrahydrobenzal glycerol, 146 parts of oxalic aciddiethyl ester, 2 parts of sodium methylate and 500 parts by volume oftoluene is heated on an oil bath maintained at about 130-150 C. Thealcohol formed is distilled off as an azeotropic mixture with toluenethrough a Raschig column of 30 cm. height. When 90% of the theoreticalamount of ethanol have passed over, the solution is filtered andevaporated to leave the oxalate as a highly viscous liquid.

For analytical purposes a specimen of the product is distilled.

B.P. 232-235 n =1.5043.

C 4 H O Calculated: C, 63.98; H, 7.61%. Found: C, 64.17; H, 7.59%.

A solution of 360 parts of the oxalate in 1200 parts of ethyl acetate isreacted for 4% hours with 350 parts of peracetic acid. The mixture iscooled, diluted with 4600 parts by volume of ethyl benzene, washed twicewith 200 parts of water on each occasion and evaporated in a water-jetvacuum. The residue is freed from the last remnants of solvent by beingheated for 3 hours at 120 C. in a high vacuum. The product contains 2.89epoxide equivalents per kg.

The epoxide compound obtained by the procedure of this example has theformula C. under 0.04 mm. Hg pressure,

EXAMPLE 3 A mixture of 297 parts of 6-methyl-A -tetrahydrobenzalglycerol, 110 parts of adipic acid, 1 part of paratoluene-sulfonic acidand 1000 parts by volume of toluene is boiled in a cyclic distillationapparatus. After 10 hours, 21 parts of water have separated.

The solution is then cooled to 30 C. and in the course of one hour 320parts of peracetic acid are added in portions. After 2 hours at 30 C.the theoretical amount of peracetic acid has been consumed. The solutionis washed with Water and 2 N-sodium carbonate solution until it is freefrom acid, dried over anhydrous sodium sulfate, filtered and evaporated,to leave a viscid resin containing 3.00 epoxide equivalents per kg.

The epoxide compound obtained by the procedure of this example has theformula 0-0112 orn-o a i I 0 0- H o 0 013-0 0 CH3 1 II CH3- A mixture of396 parts of 6-methyl-A -tetrahydrobenzal glycerol, 100 parts ofsuccinic anhydride, 1 part of 10 para-toluene-sulfonic acid and 250parts of ethyl ben zene is boiled for 20 hours in a cyclic distillationapparatus, while 15 parts of water are separated.

The succinic acid ester is epoxidized with 450 parts of peracetic acidfor 3 hours at 30 C. The solution is washed with water and 2 N-sodiumcarbonate solution until it is free from acid., dried over anhydroussodium sulfate, filtered and evaporated, to yield a viscid resincontaining 2.21 epoxide equivalents per kg.

The epoxide compound obtained by the procedure of this example has theformula 0-CH2 GHQ-O Cg i A mixture of 36.8 parts of M-tetrahydrobenzalglycerol, 400 parts of dry benzene and 20 parts of pyridine is treatedat 3 C. dropwise with 23.9 parts of sebacic acid dichloride while beingcooled with a mixture of ice and sodium chloride. The mixture is warmedup to room temperature, Washed three times with parts of water on eachoccasion, dried over anhydrous sodium sulfate and evaporated, to yield51.8 parts of sebacate of tetrahydrobenzal glycerol.

45.5 parts of the above product are dissolved in 300 parts of ethylacetate and reacted for 6 hours at 40 C. with 45 parts of peraceticacid. The cooled solution is diluted with 600 parts by volume of ethylbenzene, Washed twice with 100 parts of water on each occasion, treatedwith 900 parts by volume of ethyl benzene and evaporated. The lastremnants of the solvent are removed in a high vacuum at C. Yield: 43parts of a liquid diepoxide containing 3.00 epoxide equivalents per kg.

The epoxide compound obtained by the procedure of this example has theformula 0-011, CH -O on I I on- O \O-CH o o CHO 0 rim-o-ii-wmnii-o-dmEXAMPLE 6 A mixture of 92 parts of A -tetrahydrobenzal glycerol, 37parts of phthalic anhydride, 1 part of para-toluenesulfonic acid andparts by volume of benzene is heated in a cyclic distillation apparatusfor 5 hours at the boil. The solution is diluted with 100 parts byvolume of benzene and treated with 20 parts of sodium acetate. In thecourse of 30 minutes 106 parts of peracetic acid of 42% strength areadded While cooling and the mixture is allowed to react for one hour at30 C. while being stirred. The solution is washed twice with 200 partsof Water and twice with 40 parts by volume of saturated sodium carbonatesolution (until an alkaline reaction has been established) and againwith 50 parts of water, dried over sodium sulfate and evaporated, toleave a viscous resin containing 3.5 epoxide equivalents per kg.

The epoxide compound obtained by the procedure of this example has theformula CH2O CH o-om o H-0 O-GH O HFO- EXAMPLE 7 A mixture of 594 partsof 6-methyl-A -tetrahydrobenzal glycerol, 420 parts ofM-tetrahydrobenzoic acid methyl ester, and 21 parts of sodium methylatesolution (prepared from 2 parts of sodium and 19 parts of methanol)formed being distilled off through a 30 cm. high Raschig column. Whenthe distillation ceases, 500 parts by volume of toluene are added,whereupon an azeotropic mixture of methanol and toluene passes over at64 C. The volume distillate contains the theoretical amount of methanol.The mixture is allowed to cool, filtered and distilled. The resultingM-tetrahydrobenzoic acid ester boils at 153-158 C. under 0.2 mm. Hgpressure.

A solution of 432 parts of the above ester in 1000 parts by volume ofbenzene is treated with 60 parts of anhydrous sodium acetate. Whilestirring and cooling, 600 parts of peracetic acid of 44.6% strength areadded within 40 minutes at 30 C. The mixture is allowed to react forabout 2 hours longer at 30 C., cooled and washed three times with 350parts of ice water and twice with 300 parts by volume of 2 N-sodiumcarbonate solution. The aqueous phase is extracted with 600 parts byvolume of benzene. The solution of the epoxide is dried over sodiumsulfate, filtered and evaporated, to yield 429 parts of a thicklyliquid, colorless product containing 5.02 epoxide equivalents per kg.

The epoxide compound obtained by the procedure of this example has theformula o-om o-on o EXAMPLE 8 A mixture of 49.5 parts of 6-methyl-A-tetrahydrobenzal glycerol, 500 parts by volume of dry benzene and 32parts of pyridine is treated at 0 C. with 50.7 parts of undecylenic acidchloride while being cooled with a mixture of ice and sodium chloride.After having heated up to room temperature, the mixture is filtered andthe filtrate is washed with 200 parts by volume of 2 N-hydrochloricacid, 200 parts by volume of 2 N-sodium carbonate solution and 100 partsby volume of molar monosodium phosphate solution and evaporated.Distillation of the residue under 0.02 mm. Hg pressure yields at l60162C. the undecylenic acid ester of 6-methyl-A tetrahydrobenzal glycerol inthe form of a thinly liquid, colorless oil.

C H O Calculated: C, 72.49; H, 9.967 C, 72.53; H, 10.00%.

A mixture of 60 parts of the undecylenic acid ester, 235 parts of ethylacetate and 80 parts of peracetic acid is allowed to react for 14 hoursat 40 C. and then for 7 hours at about 30 C., after which time thetheoretical amount of peracetic acid has been consumed. The solution isdiluted with 500 parts by volume of ethylbenzene, Washed twice with 150parts of water, treated with another 250 parts by volume of ethylbenzeneand evaporated in a water-jet vacuum, to yield 60 parts of a thinlyliquid diepoxide containing 3.86 epoxide equivalents per kg.

The epoxide compound obtained by the procedure of this example has theformula O-CH Fou I'ld EXAMPLE 9 A mixture of 36.8 parts ofM-tetrahydrobenzal glycerol, 200 parts by volume of dry benzene and 25parts of pyridine is treated at 3 C. portionwise with 60.2 parts ofoleic acid chloride, then heated to room temperature and the solution ofthe ester formed is washed four times with 100 parts of water, driedover anhydrous sodium sulfate, filtered and evaporated. The residueconsists of 89.3 parts of the oleic acid ester of tetrahydrobenzalglycerol.

75.4 parts of the ester so obtained are mixed with 300 parts of ethylacetate and in the course of /2 hour treated portionwise with parts ofperacetic acid. The whole is reacted for 3 hours at 40 C. The solutionis diluted with 400 parts by volume of ethylbenzene, washed twice with100 parts of water, treated with another 800 parts by volume ofethylbenzene and evaporated. The residue is a liquid epoxide containing3.92 epoxide equivalents per kg.

The epoxide compound obtained by the procedure of this example has theformula A mixture of 921 parts of A -tetrahydrobenzal glycerol, 5 partsby volume of boron trifluoride of 48% strength in ether is heated to 55C. and treated dropwise with 462 parts of epichlorohydrin, whilemaintaining the temperature at 55 C. by external cooling. The mixture isthen allowed to cool to room temperature and neutralized with 1.8 partsof powdered sodium hydroxide. (An identical reaction product is obtainedby condensing 1 molecular proportion of epichlorohydrin with 1 molecularproportion of glycerol and acetalizing the resultingglycerolmonochlorohydrin ether with A tetrahydrobenzaldehyde) The wholereaction product is dissolved in 2500 parts of ethyl acetate and slowlytreated with 1100 parts of peracetic acid. After 6 hours at 30 C. thetheoretical amount of peracetic acid has been consumed. The solution isdiluted with 2000 parts by volume of ethylbenzene, washed with 1500parts of water, treated with 3000 parts by volume of ethylbenzene andevaporated in a water-jet vacuum, to yield a product which contains 2.64epoxide equivalents per kg.

A mixture of 1200 parts of the above monoepoxide and 2000 parts byvolume of dry benzene is treated with parts of finely powdered sodiumhydroxide while being cooled at 2025 C. After one hour the sodiumchloride formed is filtered off. The filtrate is washed with 250 partsby volume of a molar monosodium phosphate solution, dried over sodiumsulfate, filtered and evaporated, to yield a liquid diepoxide containing5.56 epoxide equivalents per kg.

The epoxide compound obtained by the procedure of this example has theformula OCHg CH o-on H2OOHgCH CHg EXAMPLE 1 1 A mixture of 297 parts of6-methyl-A -tetrahydrobenzal glycerol, 500 parts by volume of drybenzene and 1.5 parts by volume of boron trifiuoride of 48% strength inether is heated to 75 C. 1 39 parts of epichlorohydrin are stirred indropwise. By supplying slight cooling the temperature is prevented fromrising above 81 C. On completion of the addition of epicholorhydrin thewhole is allowed to cool to room temperature and in the course of 15minutes 60 parts of powdered sodium hydroxide are stirred in, whilemaintaining the temperature at 25 C. by cooling. After another 23minutes the mixture is filtered and the filtrate is evaporated, and theresidue is treated with 0.2 part by volume of glacial acetic acid andrapidly distilled (B.P. 117142 C. under 13 about 0.3 mm. Hg pressure).Fractional distillation through a Vigreux column yields the glycidylether boiling at 131-137 C. under 0.4 mm. Hg pressure. The productcontains 3.90 epoxide equivalents per kg. (:99% of the theoretical).

Analysis.C H O Calculated: C, 66.11; H, *8.72; O, 25.17%. Found: C,66.17; H, 8.80; O, 25.10%.

178 parts of the above glycidyl ether are diluted with 500 parts byvolume of benzene and treated with 15 parts of anhydrous sodium acetate.

While cooling at about 30 C., 145 parts of peracetic acid of 44.6%strength are added in portions within V2 hour. The whole is allowed toreact for 1 hour and 50 minutes longer at about 30 C. and then cooled.The benzene solution of the epoxide is Washed three times with 200 partsby volume of ice water, 200 parts by volume of 2 N-sodium carbonatesolution and 150 parts by volume of monosodium phosphate solution, andthe aqueous phases are extracted with 400 parts by volume of benzene.The combined benzene extracts are dried over anhydrous sodium sulfate,filtered and evaporated, to yield 157 parts of a thinly liquid diepoxidecontaining 6.5 epoxide equivalents per kg. (288% of the theoretical).

The epoxide compound obtained by the procedure of this example has theformula EXAMPLE 12 99 parts of the dioxolane obtained from1:2:4-butanetriol and A -tetrahydrobenzaldehyde are heated to about 45C. and treated with 0.3 part by volume of boron trifiuoride of about 48%strength in ether and dropwise with 46.3 parts of epichlorohydrin; thetemperature is allowed to rise to 83 C. 15 minutes after completion ofthe addition of epichlorohydrin 2 parts of anhydrous sodium acetate areadded, the whole is diluted with 250 parts of ethyl acetate and treatedportionwise with 111 parts of peracetic acid. After the mixture hasreacted for 6 hours at 40 C. it is diluted with 200 parts by volume ofethylbenzene, washed twice with 50 parts of water, treated with 750parts by volume of ethylbenzene and evaporated in a water-jet vacuum.

The resulting monoepoxide is dissolved in 250 parts by volume of benzeneand 20 parts of finely powdered sodium hydroxide are added. The mixtureis allowed to react for 2 hours at 2126 C. The sodium chloride formed isfiltered off and the filtrate is washed with 50 parts by volume of amolar monosodium phosphate solution, dried over anhydrous sodiumsulfate, filtered and evaporated, to yield a liquid diepoxide containing5.86 epoxide equivalents per kg.

The epoxide compound obtained by the procedure of this example has theformula EXAMPLE 13 When the meta-dioxane derivative obtained from 6-methyl-tetrahydrobenzaldehyde and 1: 1: l-trimethylolpropane is reactedas described in Example 12, a liquid diepoxide is obtained whichcontains 4.45 epoxide equivalents per kg.

The epoxide compound obtained by the procedure of this example has theformula EXAMPLE I14 113 parts of the dioxolane obtained from1:2:6-hexane triol and M-tetrahydrobenzaldehyde are reacted in thepresence of 0.3 part by volume of boron trifluoride of 48% strength inether with 46.3 parts of epichlorohydrin at C.

After cooling, the product is treated with 2 parts of anhydrous sodiumacetate and diluted with 300 parts of ethyl acetate. parts of peracetic'acid are then'added in portions and the mixture is allowed to react for3 hours at 40 C., then diluted with 1000 parts by volume ofethylbenzene, washed twice with 150 parts of water, treated with another500 parts by volume of ethylbenzene and evaporated in vacuo. The productis taken up in 500 parts by volume of benzene and dehydrohalogenated at25 C. with 20 parts of finely powdered sodium hydroxide. The mixture isfiltered and the filtrate is washed with 50 parts by volume of a molarmonosodium phosphate solution, dried and evaporated, to yield parts of:a liquid diepoxide containing 5.51 epoxide equivalents per kg.

The epoxide compound obtained by the procedure of this example has theformula A mixture of 215 parts of distilled diglycerol, 300 parts of A-tetrahydrobenzaldehyde, 750 parts by volume of benzene, 3 parts ofanhydrous zinc chloride and 3 parts by volume of phosphoric acid isboiled in a cyclic distillation apparatus While being stirred. After 4/2 hours 43 parts of water have separated. The mixture is filtered andevaporated, towards the end in a high vacuum at C., and there areobtained 430 parts of the hisdioxolane.

A solution of the above dioxolane in 1500 parts by volume of benzene istreated with 20 parts of anhydrous sodium acetate. While stirring andcooling 550 parts of peracetic acid of 44.6% strength are addedportionwise in the course of one hour at 30 C. The mixture is allowed toreact for 2 hours at 30 C. and then cooled with ice. The solution of theepoxide is washed 3 times with 300 parts of water and twice with 300parts by volume of 2 N-sodium carbonate solution until it is free fromacid. The aqueous phases are extracted with 500 parts by volume ofbenzene. The benzene phases are combined, dried over anhydrous sodiumsulfate and evaporated, to yield 399 parts of thickly liquid diepoxidecontaining 4.55 epoxide equivalents per kg.

The epoxide compound obtained by the procedure of this example has theformula o-oni our-o -ofi on O oon CH-O/ O (kHz-O-CH EXAMPLE 16 159 partsof crude diglycerol (obtained in known manner for glycerol andglycerol-a-monochlorohydrin in the presence of sodium hydroxidesolution) in 500 parts by volume of benzene are condensed with 220 partsof A -tetrahydrobenzaldehyde in the presence of 1 part of zinc chlorideand 1 part by volume of concentrated phosphoric acid in a cyclicdistillation apparatus, while 29 parts of water separate.

The filtered solution of the bis-dioxolane is treated protionwise atabout 30 C. in the course of /2 hour with 420 parts of peracetic acid.The mixture is allowed to react for 75 minutes at 30 C. and then washedwith ice water and 2 N-sodium carbonate solution until it is free fromacid. The solution is dried over anhydrous sodium sulfate, filtered andevaporated. The residue is a highly viscous resin containing 4.62epoxide equivalents per kg.

The epoxide compound obtained by the procedure of this example has theformula EXAMPLE 17 83 parts of distilled diglycerol are condensed in acyclic distillation apparatus with 130 parts of 6-methyl-Atetrahydrobenzaldehyde in the presence of 500 parts by volume ofbenzene, 0.5 part of zinc chloride and 0.5 part by volume ofconcentrated phosphoric acid, during which 15 parts of water separate.The solution is filtered and evaporated and the residue is distilled ina high vacuum, to yield 156 parts of bisacetal boiling at 189- 199 C.under 0.2 mm. Hg pressure.

A solution of 141.5 parts of the bis-acetal in 500 parts of ethylacetate is treated portionwise with 165 parts of peracetic acid. Thetemperature is maintained at 40 C., initially by cooling and then bysupplying external heat. After 3 /2 hours 97% of the theoretical amountof peracetic acid have been consumed. The mixture is cooled, dilutedwith 500 parts by volume of ethylbenzene, washed twice with 150 parts ofwater, treated with 1000 parts by volume of ethylbenzene and evaporatedunder vacuum. The last remnants of the solvent are removed in a highvacuum at 120 C. Yield: 143 parts of an epoxy resin containing 3.75epoxide equivalents per kg.

The epoxide compound obtained by the procedure of this example has theformula o-on, om-o -or1 CH- o-orr CH-O 0 CH3 (g CH3- Hr-O- H2 EXAMPLE 18this example has the formula EXAMPLE 19 112 parts ofglycerolmonotricyclodecenyl ether (adduct from dicyolopentadiene andglycerol) are condensed .in a cyclic distillation apparatus in thepresence of 0.3

part of zinc chloride, 0.3 part by volume of concentrated phosphoricacid and 500 parts by volume of henzene with 60 parts of A-tetrahydrobenzaldehyde. The

solution of the acetal formed is filtered and evaporated and the residueis distilled, to yield 152 parts of a product boiling at 165172 C. under0.02 mm. Hg pressure.

C H O Calculated: C, 75.91; H, 8.92%. Found: C. 75.80; H, 8.88%.

A mixture of 111 parts of the above acetal and 300 parts of ethylacetate is reacted for 5 hours at 40 C. with 150 parts of peraceticacid, then cooled, diluted with 500 parts by volume of ethylbenzene andwashed twice with 150 parts of water. Another 500 parts by volume ofethylbenzene are added to the solution and the mixture is evaporated ona water bath in a water-jet vacuum, to yield a viscous diepoxidecontaining 5.22 epoxide equivalents per kg.

The epoxide compound obtained by the procedure of this example has theformula o-orr,

-CH l O(l3H fem to CHFO \i/ EXAMPLE 20 A mixture of 180 parts of3-vinyl-2:4-dioxospiro(5:5) undecene-8 (prepared by acetalizing A-cyclohexene-lzldimethanol with acrolein) and 184 parts of A-tetrahydrobenzal glycerol is heated to C., and 1 part of sulfuric acidis added, whereupon an evolution of heat is observed. The temperature ismaintained for 2 /2 hours at C., first by cooling and then by heating.The acid is then neutralized with 1 part of anhydrous sodium carbonate.By heating the reaction product to 112 C. under 0.1 mm. Hg pressure only6 parts of unreacted starting materials can be distilled olf, that is tosay that the additive combination proceeds substantially quantitatively.There are obtained 353 parts of the adduct in the form of a viscous,dark liquid.

A solution of 353 parts of the above adduct in 1050 parts of benzene istreated with 25 parts of anhydrous sodium acetate and heated to 35 C. Inthe course of 20 minutes 394 parts of peracetic acid of 41.2% strengthare then added with vigorous stirring and the mixture is stirred for 2%hours at 35 C. and then cooled. The aqueous phase is separated, washedthree times with 250 parts by volume of water, neutralized with 40 partsby volume of sodium hydroxide solution of 30% strength and finallywashed twice with 150 parts by volume of water. The benzene is distilledOE and the product is freed from the last remnants of the solvent bybeing heated to C. under 0.1 mm. Hg pressure, to yield 320 parts of aviscous yellow liquid containing 4.75 epoxide equivalents per kg. ('=94%of the theoretical) and consisting substantially of the diepoxide of theformula oon,,

E 0 OOH o-orn 0 JHr-O*CH2-CHz-CH EXAMPLE 21 65 parts of the epoxy resinprepared as described in Example 3 are melted at C. with 28.9 parts ofphthalic anhydride and poured into an aluminum mould (40 x 10 x mm.).

The mixture is cured for 3 hours at 120 C., then for 3 hours at C. andfinally for 24 hours at 200 C. The resulting moulding has the followingproperties:

Bending strength 11.6 kg./sq. mm. Impact banding strength 13.5 cm.kg./sq. cm.

1 Thermal stability according to Martens "we": 130 C.

EXAMPLE 22 75 parts of the diepoxide prepared as described in Example 7and 18.8 parts of succinic anhydride are melted at 120 C. and pouredinto an aluminum mold (40 x 10 x 140 mm.).

The mixture is cured for 16 hours at 120 C., then for 6 hours at 160 C.and finally for 12 hours at 200 C. The resulting moulding has thefollowing properties:

Bending strength 9.0 kg./sq. mm. Impact bending strength 6.8 cm. kg./sq.cm. Thermal stability according to Martens 175 C.

EXAMPLE 23 65 parts of the diepoxide prepared as described in Example 15are melted with 28.4 parts of phthalic anhydride at 120130 C. and pouredinto an aluminum mould (40 x 10 x 140 mm.).

The mixture is cured for 24 hours at 140 C. and then for 24 hours at 200C. The resulting moulding has the following properties:

Bending strength 10.1 kg./sq. mm. Impact bending strength 7.9 cm.kg./sq. cm. Thermal stability according to Martens 187 C.

EXAMPLE 24 70 parts of the diepoxide prepared as described in Example 15are melted with 21.2 parts of phthalic anhydride at 120 C. The resultingmixture has at 120 C. a viscosity below 20 centipoises and after 65minutes of 1500 centipoises. The melt is poured over plates of glass toform layers 0.1 mm. and 1 mm. thick respectively and then hardened for24 hours at 140 C. and subsequently for 24 hours at 200 C. The curedfilms are clear, substantially colorless, elastic and adhere very firmlyto the support. They remain intact after having been immersed for onehour at room temperature in N-sulfuric acid, 5 N-sodium hydroxidesolution, water, acetone and chlorobenzene.

EXAMPLE 25 74 parts of the epoxy resin prepared as described in Example16 and 32.8 parts of phthalic anhydride are melted at 120 C. and pouredinto an aluminum mould (40 x x 140 mm.).

The mixture is cured for 24 hours at 140 C. The

resulting moulding has the following properties:

Bending strength 8.1 kg./sq. mm. Impact bending strength 3.8 cm. kg./sq.cm. Thermal stability according to Martens 173 C.

EXAMPLE 26 68.5 parts of the epoxy resin prepared as described inExample 10 are melted at 120 C. with 36.5 parts of phthalic anhydrideand poured into an aluminum mould (40 x 10 x 140 mm.). The mixture iscured for 4 hours 18 at C. and then for 24 hours at C. The resultingmoulding has the following properties:

Bending strength 10.9 kg./sq. mm. Impact bending strength 12.1 cm.kg./sq. cm. Thermal stability according to Martens 147 C.

What is claimed is: 1. A diepoxide of the formula in which R to R and Rare hydrogen and together R and R form the methylene group, R is amember selected from the group consisting of hydrogen and methyl, Zrepresents the hydrocarbon radical obtained by removing the hydroxylgroups from a saturated aliphatic trihydric alcohol with 3 to 6 carbonatoms and A is epoxycycloalkyl wherein the cycloaliphatic ring is asix-membered ring, the acetal ring being an at least five-membered andat most sixmembered ring.

2. The compound of the formula 0-CH O 0 3 CHr-O- No references cited.

WALTER A. MODANCE, Primary Examiner.

NICHOLAS S. RIZZO, Examiner.

1. A DIEPOXIDE OF THE FORMULA